EP2647640A1 - ß-boration Alken- und Alkyn-Zwischenstoffen - Google Patents

ß-boration Alken- und Alkyn-Zwischenstoffen Download PDF

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Publication number
EP2647640A1
EP2647640A1 EP12002520.0A EP12002520A EP2647640A1 EP 2647640 A1 EP2647640 A1 EP 2647640A1 EP 12002520 A EP12002520 A EP 12002520A EP 2647640 A1 EP2647640 A1 EP 2647640A1
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bis
alkyl
formula
compound
aryl
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Lek Pharmaceuticals dd
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Lek Pharmaceuticals dd
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Priority to EP12002520.0A priority Critical patent/EP2647640A1/de
Priority to CN201380029491.6A priority patent/CN104603142A/zh
Priority to PCT/EP2013/057159 priority patent/WO2013150125A1/en
Priority to EP13714298.0A priority patent/EP2850087B1/de
Publication of EP2647640A1 publication Critical patent/EP2647640A1/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds

Definitions

  • the present invention relates to the field of organic chemistry, and in particular to the preparation of ⁇ -borated compounds.
  • ⁇ -borated compounds can be used as intermediates in the synthesis of pharmaceutically active agents such as sitagliptin.
  • C-B bond plays an important role in synthetic chemistry.
  • Organoboranes are highly versatile precursors for the preparation of various organic compounds including active pharmaceutical ingredients such as sitagliptin. It is possible to transform a boronate group into another useful functional group with retention of configuration via different stoichiometric and catalytic reactions. It is known that C-B bond can be respectively converted to C-O bond by oxidation, C-N bond by amination, C-C bond via cross-coupling reactions and using fluorination to C-F bond formation.
  • transition-metal catalysed process providing ⁇ -borated compounds.
  • ⁇ -boration of ⁇ , ⁇ -unsaturated compounds catalyzed by different metals has received increasing attention driven especially by high synthetic potential and versatility of ⁇ -borated organoboron compounds.
  • the transition metals Pt ( Lawson, J. G.; et. al. Chem. Commun. 1997, 2051 .), Rh ( Shiomi, T.; et. al. Chem. Commun. 2009, 5987 .), Pd ( Lillo, V.; et. al. Org. Biomol. Chem. 2009, 7, 4674 .), Ni ( Hirano, K.; et al. Org.
  • catalytic systems based on a catalyst comprising a transition metal compound of CuCl in combination with diphosphine ligands in the presence of stoichiometric or catalytic amount of appropriate base (K 2 CO 3 , NaOt-Bu, KOH, etc.) are used for ⁇ -boration of variety of ⁇ , ⁇ -unsaturated compounds as shown in Scheme 1 ( Mun, S.; et al. Org. Lett. 2006, 8, 4887 ; Feng, X.; et al. Chem. Commun. 2009, 6577 ; O'Brien, J. M.; et al. J. Am. Chem. Soc.
  • the state of the art catalytic systems have the following limitations: a) additional stoichiometric or catalytic activators, usually base additives, are needed for efficiency of the process; b) ⁇ -boration, especially asymmetric version, is always performed in the presence of organic solvents such as THF, toluene, DMF, and final products are isolated also using volatile, toxic organic solvents; c) usually, also protic additives like MeOH, i -PrOH, EtOH are added for high efficiency and enhancement of the reaction; d) high catalyst loadings and in some cases special catalysts and ligands are used; e) some of the state of the art catalytic systems are substrate specific and thus provide for a narrow substrate scope only.
  • the object of the present invention is to provide an improved process for the preparation of ⁇ -borated compounds.
  • the object of the present invention is to develop a simple and environmentally benign process.
  • the present invention relates to a process for preparation of a compound of formula II,
  • the above procedural concepts provide for efficient and selective ⁇ -boration of alkene compounds of formula I and alkyne compounds of formula III respectively. It was surprisingly found that the boration reaction can be carried out in a reaction mixture which is free or essentially free of organic solvent(s), wherein reaction rate and/or conversion of the starting material is significantly improved compared to ⁇ -boration reactions carried out in pure organic solvent(s) or mixtures of organic solvent(s) and water in which mixtures the amount of organic solvent predominates the amount of water.
  • considerable amounts of harmful or even toxic organic solvent(s) can be saved, preferably it can be dispensed with organic solvent(s).
  • the catalytic system is in the form of a salt essentially consisting of a copper cation in oxidation state (I) or (II) and at least one anion selected from the group consisting of carbonate (CO 3 2- ), sulfate (SO 4 2- ), nitrate (NO 3 - ), phosphate (PO 4 3- ), hydroxide (OH - ) acetate (OAc - ) and tert-butoxide (O t -Bu - ), or the catalytic system is in the form of copper oxide in which copper has oxidation state (I) or (II) (Cu 2 O or CuO); more preferably the catalytic system is in the form of a salt essentially consists of a copper cation in oxidation state (I) or (II) and at least one anion selected from the group consisting of carbonate (CO 3 2- ), sulfate (SO 4 2- ), nitrate (NO 3 -
  • ⁇ -boration processes particularly suitable catalytic systems are provided, since the catalytic system in the form of a salt or an oxide renders possible to dispense with additional base activators which are typically applied in conventional ⁇ -boration processes.
  • copper carbonate (CuCO 3 ) represents a readily available and surprisingly effective catalytic system, as acting as a metal and a base activator in one molecule.
  • the catalyst system is formed in situ by using a copper salt and a base, wherein the salt is selected from carbonate (CO 3 2- ), sulfate (SO 4 2- ), nitrate (NO 3 - ), phosphate (PO 4 3- ), hydroxide (OH - ) acetate (OAc - ) and tert -butoxide (O t -Bu - ), and the base is selected from Na 2 CO 3 , K 2 CO 3 , Cs 2 CO 3 and MgCO 3 .
  • the salt is selected from carbonate (CO 3 2- ), sulfate (SO 4 2- ), nitrate (NO 3 - ), phosphate (PO 4 3- ), hydroxide (OH - ) acetate (OAc - ) and tert -butoxide (O t -Bu - )
  • the base is selected from Na 2 CO 3 , K 2 CO 3 , Cs 2 CO 3 and MgCO 3 .
  • the boronating agent is selected from the group consisting of boronic esters, alkyl boranes and alkyl-aryl boranes, preferably chiral boronic esters, chiral alkyl borane and chiral alkyl-aryl boranes.
  • the boronating agent is selected from the group consisting of bis(pinacolato)diboron, catecholborane, bis(neopentyl-glycolato)diboron, bis(hexylene-glycolato)diboron, ( S )-bis(pinene)borane, ( R )-bis(pinene)borane, bis(terpenoyl)borane, pinacolatoborane, bis(catecholato)diboron, disamyiborane9-borabicyclo[3.3.1]nonane (9-BBN), diisopinocampheylboran (Ipc 2 BH), preferably bis(pinacolato)diboron.
  • the boronating agent is suitably selected in view of regioselectivity of the reaction and/or subsequent convertibility into another functional group.
  • the compound of formula I is selected from the group consisting of and the compound of formula III is selected from the group consisting of
  • the catalytic system is present in an amount of 1-20 mol%, preferably 1.5-16 mol%, more preferably of 2-12 mol%, and even more preferably 3-8 mol% relative to the compound of formula I or III.
  • the boronating agent is present in an amount of 1.05-1.5 equivalents, preferably 1.1-1.3 equivalents relative to the compound of formula I or III.
  • the reaction mixture of the present processes comprises at least one ligand.
  • the presence of a ligand improves reaction rate and/or conversion of the substrate of the reaction.
  • the at least one ligand is present in an amount of 1-25 mol%, preferably 1.5-18 mol%, more preferably 2-14 mol%, even more preferably 2.5-12 mol%, and in particular 3-6 mol% relative to compound of formula I or II.
  • the at least one ligand is selected from monophosphine ligands selected from triphenylphosphine, trimethylphosphine, tricyclohexylphosphine, tributylphosphine, tri-( o- tolyl)-phosphine, tri-(2-furyl)phosphine, tris(dimethylamino)-phosphine, tribenzylphosphine, tripyrolydinophosphine, tris(4-methoxyphenyl)phosphine and any combination thereof.
  • monophosphine ligands selected from triphenylphosphine, trimethylphosphine, tricyclohexylphosphine, tributylphosphine, tri-( o- tolyl)-phosphine, tri-(2-furyl)phosphine, tris(dimethylamino)-phosphine, tribenzylphosphine, tripyroly
  • the ligand is diphosphine ligand selected from 1,2-bis(diphenyl-phosphino)benzene, 1,1,-bis(di-tert-butylphosphino)ferrocene, (oxydi-2,1-phenylene)bis-(diphenylphosphine), and any combination thereof.
  • the ligand is N,O -containing ligand, in particular D -glucozamine.
  • the ligand is O -containing ligand, in particular D -glucose.
  • the ligand is chiral and selected from ( R )-2,2'-bis(diphenylphosphino)-1,1-binaphthalene, ( S )-2,2'-bis(diphenylphosphino)-1,1-binaphthalene, ( S , R )-(diphenylphosphino)-ferrocenyl-ethyldi- tert -butylphosphine, ( R , S )-(diphenylphosphino)-ferrocenyl-ethyldi- tert -butylphosphine, ( S )-1-( S p)-2-[2-(diphenylphosphino)-phenyl]-ferrocenyl-ethylbis[3,5-bis(trifluoromethyl)phenyl]phosphine, ( R )-1-( R p)-2-[2-(diphenylphosphino)
  • Chiral ligands are particularly advantageous, since they provide for enantiomeric excess in the products of compound of formula II and IV respectively.
  • the reaction mixture further comprises at least one chiral ligand.
  • a chiral ligand for high enantioselectivity of up to 95% ee in water as the solvent. It is a common general knowledge that asymmetric transformations especially enantioselective catalysis in water is problematic, due to low solubility and incompatibility of chiral catalysts with water.
  • step (b) is carried out without adding an additional base activator.
  • reaction mixture of step (b) further comprises a surfactant
  • the surfactant is selected from the group consisting of nonionic polyethyleneglycols (PEGs) comprising 7 to 30 ethylene glycol units and salts of C8-C15 fatty acids or C8-C15 alkylsulfates, preferably the surfactant is selected from the group consisting of tocopheryl polyethylene glycol succinate (TPGS), sodium dodecylsulfate (SDS) and Triton X-100.
  • PEGs nonionic polyethyleneglycols
  • TPGS tocopheryl polyethylene glycol succinate
  • SDS sodium dodecylsulfate
  • Triton X-100 Triton X-100
  • step (b) is carried out at a temperature of 20 °C to 100 °C, preferably of 22 °C to 60 °C, more preferably 24 °C to 50 °C.
  • the products are isolated without using any organic solvents, preferably by means of distillation or by precipitation or separation from water in a seperatory funnel.
  • a chiral boronating agent and/or a chiral ligand is applied in order to obtain a compound of formula II having an enantiomeric excess of at least 60%, preferably an enantiomeric excess of at least 85%, more preferably the enantiomeric excess is at least 90%, even more preferably at least 95% and in particular at least 98%.
  • compound of formula II can be obtained in an advantageous high enantiomeric excess or even in enantiomerically pure state.
  • compounds of formula I and II are in the form of compound of formula Is and compound of formula IIs respectively, and the chiral ligand is as defined in item (21). It was surprisingly found that compound of formula IIs can be obtained in high enantiomeric excess when a ligand as defined in item (21) is applied.
  • a compound of formula IVa to IVd is respectively obtained having the structural formula
  • a process for the preparation of sitagliptin having the structural formula comprises the steps of:
  • the above mentioned aspect provides for a particularly advantageous process for preparing sitagliptin owing to the application of the present procedural aspects of ⁇ -boration and the beneficial effects involved therewith.
  • R 11 of compound of formula II' is substituted or unsubstituted C1-C6 alkyl, C6-C12 aryl or C7-C12 alkylaryl, more preferably unsubstituted C1-C3 alkyl.
  • bls(pinacolato)diboron is applied as boronating agent, and in compound of formula II or IV, R 5 and R 6 together with boron form a pinacolatoboron moiety having the structure
  • the process for preparation of compound of formula II or the compound of formula IV according to item (1) or (3) is used in the process of transformation of the C-B bond to C-O, C-N, C-S bond and C-X bond, wherein X is F, Cl, Br, I.
  • the process for preparation of compound of formula II or the compound of formula IV according to item (1) or (3) is used in the process of transformation of the GB bond at the chiral center to C-O, C-N, C-S bond and C-X bond, wherein X is F, Cl, Br, I, respectively with the retention of configuration at the chiral center.
  • Example 1 ⁇ -Boration of 1-(trifluoromethyl)-4-vinylbenzene to 4,4,5,5-tetramethyl-2-(4-trifluoromethyl)phenethyl)-1,3,2-dioxoborolane in water:
  • Example 2 ⁇ -Boration of 1-metoxy-4-vinylbenzene to 2-(4-methoxyphenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxoborolane in water:
  • Example 3 ⁇ -oration of 1-phenyl-ethene to 4,4,5,5-tetramethyl-2-phenethyl-1,3,2-dioxaborolane in water:
  • alkene 1-phenyl-ethene (1.0 mmol) was slowly dropped into the reaction system and such reaction mixture was intensively stirred at 30 °C for 24 hours.
  • the reaction mixture was diluted with brine (5 mL) and extracted with EtOAc (2 x 35 mL). Combined organic layers were again washed with brine (30 mL), dried over Na 2 SO 4 and organic solvent was removed under the reduced pressure.
  • Example 4 Ligandless ⁇ -boration of model alkene 1-phenyl-ethene to 4,4,5,5-tetramethyl-2-phenethyl-1,3,2-dioxaborolane in water:
  • Example 6 ⁇ -Boration of 1,2-diphenylethylene to (2)-2-(1,2-diphenylvinyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane in water:
  • Example 7 ⁇ -Boration of 1-phenyl-propyne to (2)-4,4,5,5-tetramethyl-2-(1-phenyl-prop-1-en-2-yl)-1,3,2-dioxaborolane in water:
  • alkyne 1-phenyl-propyne (1.0 mmol) was slowly dropped into the reaction system and such reaction mixture was intensively stirred at 27 °C for 24 hours.
  • the reaction mixture was diluted with brine (5 mL) and extracted with EtOAc (2 x 40 mL). Combined organic layers were again washed with brine (30 mL), dried over Na 2 SO 4 and organic solvent was removed under the reduced pressure.
  • Example 8 ⁇ -Boration of 1-phenyl-acethylene to ( E )-4,4,5,5-tetramethyl-2-styryl-1,3,2-dioxaborolane in water:
  • Example 10 ⁇ -Boration of ( E )-ethylcrotonate to ethyl 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-butanoate in water:
  • the reaction mixture was diluted with brine (5 mL) and extracted with EtOAc (2 x 40 mL). Combined organic layers were again washed with brine (30 mL), dried over Na 2 SO 4 and organic solvent was removed under the reduced pressure.
  • Example 12 ⁇ -Boration of ( E )-ethylcrotonate to ethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-butanoate in water in the presence of D -glucose as ligand:
  • Example 13 ⁇ -Boration of ( E )-ethylcrotonate to ethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-butanoate in water in the presence of D -glucosamine as ligand:
  • N,O -containing-ligand D -glucosamine hydrochloride (0.035 mmol, 3.5 mol% according to starting material) which was first neutralized with aqueous solution of NaOH. Afterwards catalyst CuCO 3 (0.03 mmol, 7.50 mg, 3 mol% according to starting material) was added followed by 2.6 mL of deionized water and reaction mixture was vigorously (900 rpm) stirred at ambient temperature for 30 min. The boronating reagent bis(pinacolato)diboron (1.1 mmol, 280.0 mg, 1.1 equiv.) was added in one portion and such reaction mixture was stirred at ambient temperature for 45 min.
  • Example 14 ⁇ -Boration of N,N -dimethylacrylamide to N,N -dimethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-propanamide in water in the presence of D-glucosamine as ligand:
  • N,O -containing ligand D -glucosamine hydrochloride (0.035 mmol, 3.5 mol% according to starting material) which was first neutralized with aqueous solution of NaOH. Afterwards catalyst CuCO 3 (0.03 mmol, 7.50 mg, 3 mol% according to starting material) was added followed by 2.5 mL of deionized water and reaction mixture was vigorously (900 rpm) stirred at ambient temperature for 30 min. The boronating reagent bis(pinacolato)diboron (1.1 mmol, 280.0 mg, 1.1 equiv.) was added in one portion and such reaction mixture was stirred at ambient temperature for 45 min.
  • Example 15 ⁇ -Boration of methyl acrylate to methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-propanoate in water:
  • Example 16 ⁇ -Boration of 1,1,1,3,3,3-hexafluoropropan-2-yl acrylate to 1,1,1,3,3,3-hexafluoropropan-2-yl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanoate in water:
  • Example 17 ⁇ -boration of ( E )-1,5-diphenylpent-1-en-3-on to 1,5-diphenyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yi)-pentan-3-on in water:
  • Example 18 ⁇ -Boration of vinyl cinnamate to vinyl 3-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanoate in water:
  • Example 19 ⁇ -Boration of 1-phenyl-vinyl-sulfone to 4,4,5,5-tetramethyl-2-(2-(methylsulfonyl)ethyl)-1,3,2-dioxoborolane in water:
  • Example 20 ⁇ -Boration of vinyl methylacrylate to vinyl-2-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanoate in water:
  • Example 21 ⁇ -Boration of 3-methylenedihydrofuran-2(3 H )-one to 3-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)dihidrofuran-2(3H)-one in water:
  • Example 22 ⁇ -Boration of 3-methylcyclohex-2-enone to 3-methyl-3-(4,4,5,6-tetramethyl-1,3,2-dioxaborolan-2-yl)-cyclohexanone in water:
  • Example 23 Copper salt mediated ⁇ -boration of ( E )-ethylcrotonate to ethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborotan-2-yl)-butanoate in aqueous medium:
  • Example 24 Asymmetric ⁇ -boration of ( E )-methyl 4-(2,4,5-trifluorophenyl)but-2-enoate to optical active methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-4-(2,4,5-trifluorophenyl)butanoate in water

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EP12002520.0A 2012-04-06 2012-04-06 ß-boration Alken- und Alkyn-Zwischenstoffen Withdrawn EP2647640A1 (de)

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Application Number Priority Date Filing Date Title
EP12002520.0A EP2647640A1 (de) 2012-04-06 2012-04-06 ß-boration Alken- und Alkyn-Zwischenstoffen
CN201380029491.6A CN104603142A (zh) 2012-04-06 2013-04-05 烯烃和炔烃中间体的β-硼化
PCT/EP2013/057159 WO2013150125A1 (en) 2012-04-06 2013-04-05 ß-BORATION OF ALKENE AND ALKYNE INTERMEDIATES
EP13714298.0A EP2850087B1 (de) 2012-04-06 2013-04-05 Ss-boration alken- und alkyn-zwischenstoffen

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106366105A (zh) * 2016-08-04 2017-02-01 大连理工大学 一种二氟烯丙基硼酸酯的制备方法及其应用
CN106946922A (zh) * 2017-05-08 2017-07-14 华侨大学 一种1,1,2‑三硼化合物的合成方法

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106366105A (zh) * 2016-08-04 2017-02-01 大连理工大学 一种二氟烯丙基硼酸酯的制备方法及其应用
US10494383B2 (en) 2016-08-04 2019-12-03 Dalian University Of Technology Method for preparing difluoroallylboronate and application thereof
CN106946922A (zh) * 2017-05-08 2017-07-14 华侨大学 一种1,1,2‑三硼化合物的合成方法
CN106946922B (zh) * 2017-05-08 2019-05-03 华侨大学 一种1,1,2-三硼化合物的合成方法

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